EP0154189A2 - Poudres de polymères préparés en émulsion et procédé pour en préparer - Google Patents

Poudres de polymères préparés en émulsion et procédé pour en préparer Download PDF

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Publication number
EP0154189A2
EP0154189A2 EP85101320A EP85101320A EP0154189A2 EP 0154189 A2 EP0154189 A2 EP 0154189A2 EP 85101320 A EP85101320 A EP 85101320A EP 85101320 A EP85101320 A EP 85101320A EP 0154189 A2 EP0154189 A2 EP 0154189A2
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EP
European Patent Office
Prior art keywords
dispersion
emulsion polymer
dispersions
particles
solids content
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Ceased
Application number
EP85101320A
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German (de)
English (en)
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EP0154189A3 (fr
Inventor
Wolfgang Dr. Klesse
Hubert Rauch
Werner Dr. Siol
Norbert Dr. Sütterlin
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Publication of EP0154189A2 publication Critical patent/EP0154189A2/fr
Publication of EP0154189A3 publication Critical patent/EP0154189A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the invention relates to powdered emulsion polymers based on acrylic monomers and a process for their preparation by spray drying.
  • the spray drying of aqueous dispersions is a technically customary process for obtaining dry powders from emulsion polymers based on acrylic monomers.
  • DE-OS 21 01 808 discloses the production of PVC processing aids by spray drying an aqueous dispersion of an emulsion polymer of methyl methacrylate and acrylic acid esters. Spray drying below the glazing temperature gives powder granules of loosely aggregated fine particles which, when incorporated into plasticized PVC, are distinguished by a particularly uniform digestion.
  • DE-AS 27 22 752 describes the production of plastisols from an emulsion polymer whose latex particles are made up of a softer core and a harder shell, and from a plasticizer for the polymer.
  • the aqueous dispersion of the emulsion polymer is converted into a dry powder by spray drying at 50-100 ° C.
  • powders of emulsion polymers obtained by spray drying an aqueous dispersion are used as binders in the preparation of film-forming coating agent solutions for pharmaceutical forms.
  • the emulsion polymers are in such a way from a mixture of water-soluble, partly. salt-forming monomers and water-insoluble comonomers built up that they are water-soluble in a part of the pH range between pH 1.5 and 8. In this spray drying process, too, it is important that the latex particles in the individual powder granules do not melt completely, but are loosely aggregated and easily broken down.
  • the powders of emulsion polymers made from acrylic monomers obtained by spray drying have some disadvantages.
  • Their bulk density is generally between 300 and 350 g / l.
  • the bulk density is thus far below the theoretical value that a densest packing of spherical powder particles with a density of 1 g / ml should have, namely 740 g / l.
  • the low bulk density is due to internal voids in the powder granules.
  • the granules have an average size of about 20 to 150 ⁇ m and are built up from an aggregation of a few thousand to a few million latex particles.
  • the low bulk density means a large storage and transport volume.
  • the bulk density can be increased by glazing the latex particles in the individual granules, but the application properties are adversely affected.
  • the powders immediately produced by spray drying always contain a considerable amount of fine dust.
  • the fine dust is whirled up and gets into the breathing air, which is unsafe in terms of work hygiene. Therefore, the permissible limit values for the fine dust content in the air of a workplace have recently been reduced. It is technically complex to separate the fine dust by sieving or air separation.
  • sprayable dispersions can be used for spray drying. They often have to be diluted with water to a lower solids content in order to reduce the viscosity. However, the added water must be evaporated again during spray drying and requires additional energy.
  • the invention has for its object to increase the bulk density of powdery emulsion polymers, which are largely composed of acrylic monomers and have a glass transition temperature not below 45 ° C, and their content Reduce fine dust without adversely changing the desired fine structure of the powder grains.
  • Another object of the invention is to reduce energy consumption and increase productivity in the manufacture of the powders by spray drying.
  • the original latex particles of the underlying emulsion polymer can be seen at 10,000- to 15,000-fold magnification, for example in a transmission electron microscope or in a scanning electron microscope image, in the powder particles or in the fragments produced by grinding. If the distinction between individual particles becomes more difficult with increasing glazing, the matrix composed of larger and smaller latex particles and the size ratio of the particles can be recognized.
  • the bimodal particle size distribution can be recognized from the underlying aqueous dispersion of the emulsion polymer if the volume distribution of the particle size is determined.
  • the ultracentrifuge method according to Scholtan and Lange is particularly suitable for this.
  • the volume distribution shows two separate maxima at different particle sizes. The maxima are preferably at particle sizes which differ by a factor between 1.2 and 20, preferably 1.8 and 8.
  • the bulk density of the powders produced according to the invention is 10 to 30% higher than that of a similar unimodal emulsion polymer which has been spray-dried under the same conditions.
  • the increase in the bulk density is greater the higher the solids content of the dispersion used for spray drying.
  • the fine dust content in spray-dried powders from unimodal dispersions is generally between 5 and 10% by weight, in some cases even higher.
  • the particulate matter content of powders made up of very loosely aggregated fine particles is particularly high.
  • the fine dust content is reduced to less than 5% by weight, in favorable cases even less than 1% by weight.
  • a grain size distribution curve for a typical powder according to the invention is shown in FIG. 1. According to the DFG Communication XIX on "Maximum caries concentrations and biological working substance tolerance values" (1983), all particles with a size of less than 10 ⁇ m count towards the fine dust content. predominantly they are under 5 ⁇ m in size.
  • dispersions of a limited viscosity can be used, which depends on the structure of the spray drying system. Since the viscosity of a dispersion increases with its solids content, the viscosity limit also means a limit to the solids content. Dispersions with a viscosity above the limit must be diluted with water to the just sprayable viscosity. As is known, bimodal dispersions have a lower viscosity than unimodal dispersions with the same solids content, or a higher solids content with the same viscosity. It follows from this that bimodal dispersions of higher solids content can be processed in the same spray drying system than unimodal dispersions. This considerably reduces the energy required for the evaporation of the water.
  • the highly concentrated bimodal dispersions which are particularly advantageous because of the reduction in fine dust content and the increase in the bulk density, can still be processed well in most technical spray drying systems.
  • the powders according to the invention are not only more economical to produce, but also offer the user considerable advantages owing to the reduced fine dust development and the lower storage and transport volume. They are also much easier to mix homogeneously with powders of higher bulk density, such as PVC powder.
  • the powders are therefore used with advantage in all areas where spray-dried emulsion polymer powders have previously been used.
  • Typical areas of application for spray-dried emulsion polymers based on acrylic monomers are modifiers to improve the plastic processability or to increase the impact strength of thermoplastic molding compounds, in particular PVC, quickly soluble coating and binding agents for paints or printing inks based on organic solvents, plastisols, and blockage-preventing additives for pigment-free top coats for synthetic leather and the like. Specific examples of such applications have already been mentioned in the "prior art" section.
  • Emulsion polymers are understood to mean the polymers produced in the form of a latex in an aqueous phase by free-radical polymerization using water-soluble initiators of non-or at most limited water-soluble ethylenically unsaturated monomers or monomer mixtures.
  • the emulsion polymer is predominantly, generally more than 70% by weight, composed of acrylic monomers or their mixture with styrenes.
  • Acrylic monomers are understood to mean derivatives of acrylic and methacrylic acid. The most important group includes these acids themselves, their nitriles and the alkyl esters, which usually have 1 to 20 carbon atoms in the alkyl radical contain.
  • the acrylic monomers of this group preferably form at least 50, and particularly preferably at least 80,% by weight of the emulsion polymer.
  • acrylic monaners which can usually only be considered in small proportions for modification and only in exceptional cases as main components of the emulsion polymer, are acrylamide, methacrylamide, their N-mathylene compounds and N-methylol ether, hydroxyalkyl esters and hydroxyalkylamides of acrylic or methacrylic acid, ethers of these hydroxy compounds, Glycidyl esters of acrylic or methacrylic acid, aminoalkyl esters and aminoalkylamides of acrylic or methacrylic acid and their quaternization products.
  • styrenes can form a significant proportion of the emulsion polymer. In addition to styrene itself, this includes vinyltoluene, ⁇ -methylstyrene and other alkylated styrenes.
  • copolymerizable, ethylenically unsaturated, free-radically polymerizable or copolymerizable compounds can therefore be involved in the structure of the emulsion polymer, generally to an extent of less than 30% by weight.
  • these include, for example, maleic acid, maleic anhydride, itaconic acid, vinylimidazole, vinylpyrrolidone, vinyl esters and vinyl halides.
  • Crosslinking monomers which contain two or more polymerizable carbon double bonds can also be involved in the structure.
  • the molecular weight of the emulsion polymer can be reduced by regulators, such as mercaptans or thioglycolic acid esters.
  • the emulsion polymer contains two particle families with clearly separated maxima in the particle size distribution curve. In order to have a clearer effect, none should of the two particle families form a proportion of less than 5% by weight of the total emulsion polymer.
  • the finer latex particles have a size between 0.02 and 1.7 ⁇ m, preferably between 0.02 and 0.5 ⁇ m and form a proportion of 5 to 80% by weight, preferably 10 to 50% by weight. while the coarser particles make up the remaining portion and have a size between 0.2 to 2 microns, preferably 0.2 to 0.6 pm.
  • the emulsion polymer has a glass transition temperature above 45 ° C., preferably above 55 ° C.
  • the glass temperature can be determined according to DIN 7724. If the determination of the glass transition temperature for an emulsion polymer results in several transition areas at different temperatures, it is sufficient if the polymer material, which forms the outer shell of the individual latex particles, does not show up below 45 ° C. through a transition area. Dispersions of polymers with a glass transition temperature below are no longer economically feasible in technical spray drying systems.
  • the glass transition temperature is determined in a manner known per se by the selection of the monomers involved in the construction of the emulsion polymer.
  • Bimodal dispersions from which the powders according to the invention can be produced can be prepared in two different ways, namely by mixing two dispersions of different particle size or by stepwise polymerization.
  • two are unimodal Dispersions prepared separately and then mixed in such a ratio that each of the two dispersions contributes a particle family of the desired size and amount to the resulting bimodal dispersion.
  • the particle size maxima of the separately produced dispersions must be in accordance with the requirements applicable to the bimodal dispersion to be produced with significantly different particle sizes.
  • the particle size and the particle size distribution can be set in a targeted manner in the production of unimodal dispersions, above all by the emulsifier concentration during the particle formation phase at the beginning of the emulsion polymerization; see. DE-PS 1 804 159.
  • the so-called seed latex method is frequently used for the production of coarse-particle dispersions, in which a latex known by particle number and size is introduced and its particles are allowed to grow to the desired size by further polymerization without the formation of new particles.
  • the unimodal dispersions can be prepared with solids contents of up to about 60% by weight; a suitable method is described in DE-AS 19 10 488.
  • the viscosities of the unimodal dispersions can optionally be above the range suitable for spray drying; this applies in particular to the fine-particle dispersion.
  • Their bimodal mixture usually has a lower viscosity.
  • the mixing process offers the possibility of using dispersions of polymers with different compositions, which may result in special effects.
  • the dispersion can be sprayed into an aerosol using a two-fluid nozzle, a pressure nozzle or a rotating perforated disc.
  • dispersions with viscosities of up to 2000, if necessary up to 4000 mPa.s, can generally be processed.
  • the solids content is generally as high as possible for production reasons, preferably above 50% by weight or 45% by volume. Often it is difficult - especially in the case of emulsifying dispersions - to have solids contents above 55% by weight (or 50% % By volume), in particular above 58% by weight (or 53% by volume), but the use of these highly concentrated dispersions is particularly advantageous for the present invention.
  • the percentages relate to the polymer proportion, based on the total dispersion. Both the economic advantages in the production and the technological advantages in the use of the powders according to the invention become more apparent the higher the solids content of the dispersions used. In addition to the solids content, the emulsifier also has an influence on the grain structure of the powder.
  • the air entering the dryer usually has a temperature in the range from 110 to 250 ° C., in particular 130 to 200 ° C., and is thus far above the glass transition temperature of the polymer, which is usually not above 100 ° C.
  • the dispersion droplets still contain water, their temperature does not rise above about 50 to 60 ° C. Only when the water has completely evaporated does the temperature of the powder granule rise to the temperature of the surrounding air.
  • the air temperature in the dryer drops steadily from the air inlet to the air outlet by releasing the heat of evaporation for the evaporating water.
  • the final temperature results from the quantity and temperature of the air blown in and from the quantity of dispersion which is passed through and can be influenced by these variables.
  • the maximum temperature that the powder granules reach in the dryer and which is usually at the air outlet has a considerable influence on the properties of the powder granules. If the temperature is well above the glass transition temperature, the latex particles sinter into one in each powder grain largely homogeneous mass together. The grain is hard and brittle, only slowly soluble in solvents and, when incorporated into a molding compound melt, can only be distributed with a long time after plasticizing. With such powders, the advantages of the invention can no longer be clearly seen. The bulk density is still higher than at a lower temperature, but a bulk density of almost the same size can also be achieved if a unimodal dispersion is spray-dried to form completely glazed granules.
  • the average grain size of the powders according to the invention is between 20 to 500 ⁇ m and preferably between 30 and 150 ⁇ m.
  • the amount of fine dust depends in any case on the spray conditions and the properties of the spray drying system. Under the same spray drying conditions, the amount of fine dust in processing bimodal dispersions is always considerably lower than when processing comparable unimodal dispersions of the same viscosity. In favorable cases, the fine dust content is reduced to half to a quarter of the value for unimodal dispersions. The difference is all the greater, the less glazed the granules and the smaller their size.
  • the bulk densities of typical powders according to the invention are between 350 and 550 g / 1, while under comparable spray drying conditions unimodal dispersions can only achieve bulk densities of 300 to 400 g / 1.
  • the bulk density When changing from unimodal to bimodal dispersions of the same viscosity, the bulk density generally increases by 10 to 30%.
  • An emulsion consisting of 8.316 kg of methyl methacrylate, 9.504 kg of butyl acrylate, 0.063 kg of the above-mentioned emulsifier, 0.028 kg of the above-mentioned initiator and 18 kg of dist. Water added. The mixture is then kept at 80 ° C. for 2 hours, then cooled to room temperature. A coagulate-free dispersion having a solids content of 30% by weight is obtained; pH 2.5; Viscosity. 43 mPa sec, particle size: 0.044 ⁇ m.
  • a coagulate-free dispersion having a solids content of 30% by weight, pH value of 5.5, viscosity of 45 mPa.s and a particle size of 0.060 ⁇ m is obtained.
  • a dispersion is obtained with a solids content of 50% by weight, a pH of 3.4, a viscosity of 9200 mPa.s and a particle size of 0.12 ⁇ m. Before the spray drying, the dispersion was diluted to a solids content of 45%.
  • Process C is repeated with 68 g instead of 4 g paraffin sulfonate and results in a dispersion with a solids content of 50% by weight, a pH of 3.3, a viscosity of 15,200 mPa.s and a particle size of 0.064 ⁇ m. Before the spray drying, the dispersion is diluted to a solids content of 40%.
  • Process C is repeated with 6.8 g instead of 4 g paraffin sulfonate and results in a dispersion with a solids content of 49.6%, a pH of 3.3, a viscosity of 46 mPa.s and a particle size of 0.33 ⁇ m.
  • a coagulate-free dispersion having a solids content of 50% by weight, a pH of 7.8, a viscosity of 260 mPa.s and a particle size of 0.23 ⁇ m is obtained.
  • the emulsion 2 is then added within 90 minutes. After the end of the feed, the batch is kept at 80 ° C. for 2 hours, then cooled to room temperature.
  • a coagulate-free dispersion having a solids content of 50% by weight, a pH of 7.0, a viscosity of 94 mPa.s and a particle size of 0.27 ⁇ m is obtained.
  • the emulsion 2 is then added within 90 minutes.
  • a coagulate-free dispersion having a solids content of 40% by weight, a pH of 6.8, a viscosity of 26 mPa.s and a particle size of 0.11 ⁇ m is obtained.
  • Solids content 50% by weight; Viscosity 35 mPa.s; Particle diameter 0.30 ⁇ m.
  • a dispersion is obtained with a solids content of 60% by weight, a viscosity of 3600 mPa.s and a particle size of 0.37 ⁇ m. Before spray drying, the dispersion is distilled with dist. Diluted water to a solids content of 58%.
  • Solids content 50% by weight; Particle diameter 0.36 ⁇ m; Viscosity 40 mPa.s; pH 4.4.
  • a coagulate-free dispersion with a solids content of 50% by weight, a pH of 4.2 and a viscosity of 23 mPa.s.
  • the dispersion contains 25% of particles with a diameter of 0.12 ⁇ m and 75% of particles with a diameter of 0.39 ⁇ m.
  • a dispersion is obtained with a solids content of 60% by weight, a pH of 3.2 and a viscosity of 760 mPa.s.
  • the dispersion contains 18% particles with a diameter of 0.13 ⁇ m and 82% particles with a diameter of 0.39 ⁇ m.
  • a dispersion is obtained with a solids content of 57% by weight, a pH of 7.2 and a viscosity of 135 0 mPa.s.
  • the dispersion contains 66% of particles with a diameter of 0.17 ⁇ m and 34% of particles with a diameter of 0.30 ⁇ m.
  • T The procedure is the same as for P. Add 20 g of seed latex A 75 minutes after the start. Solids content 60% by weight; pH 3.2; Viscosity 1300 mPa.s; 27% of the particles have a diameter of 0.12 ⁇ m, 73% have a diameter of 0.34 ⁇ m.
  • V The procedure is the same as for M, but the following approach is used: After 50 minutes of the feed, 20 g of the seed latex A are added dropwise within 10 minutes.
  • Solids content 57% by weight; Viscosity 750 mPa.s; pH 7.0; 58% of the particles have a diameter of 0.18 ⁇ m, 42% of the particles have a diameter of 0.25 ⁇ m.
  • the dispersion contains 20% of particles with a diameter of 0.13 ⁇ m and 80% of particles with a diameter of 0.40 ⁇ m.
  • Water is initially charged at 80 ° C., within 4 hours one previously consisting of 40.48 kg of ethyl methacrylate, 3.52 kg of 2-hydroxypropyl acrylate, 0.308 kg of dodecyl mercaptan, 0.243 kg of the above-mentioned emulsifier, 43.2 g of the above-mentioned initiator and 23 , 7 kg of water emulsion at 80 ° C stirred. 45 minutes after the start of the feed, 0.80 kg of seed latex B are added to the dispersion within 10 minutes without interrupting the emulsion feed. After the end of the feed, the batch is kept at 80 ° C. for 2 hours, then cooled to room temperature.
  • the dispersion contains 50% of particles with a diameter of 0.20 ⁇ m and 50% of particles with a diameter of 0.41 ⁇ m.
  • Example 6 a spray drying system is used to dry the dispersion, which is equipped with a rapidly rotating atomizer disc (20,000 rpm) and through which air flows at 125-150 ° C. in cocurrent.
  • the quantity ratio of the dispersion to the air is set so that the spray material leaves the system at an air outlet temperature of 65-75 ° C. in the form of a dry, finely divided, white to translucent powder containing no glassy constituents.
  • the throughput of dry air is 400 m 3 / h.
  • Dispersions G and R were processed in an industrial spray drying system. It is equipped with a rapidly rotating open atomizer disc (10,000 rpm) and is operated in co-current with the sprayed material with air at 190 ° C. The dispersion / air ratio is set so that an air outlet temperature of 80 ° C is reached.
  • the throughput of dry air is 10,000 m 3 / h.
  • bimodal dispersions produced by two-stage polymerization are processed.
  • the dispersions are characterized in Table I.
  • the inlet temperature TE and the outlet temperature TA of the dry air and the bulk density of the powder obtained are given for the spray drying process.
  • the ratio of the bulk densities V b from the bimodal dispersions and V from the corresponding unimodal comparative dispersions is given in the last column.
  • the unimodal dispersions C to 0 were spray dried.
  • the dispersions are characterized in Table II.
  • the information about the spray drying process corresponds to that of Table I.
  • a transmission electron micrograph of the powder produced in Example 1 was taken on an ultra-thin section, which is shown in FIG. 2; Magnification 10,500 times.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polymerisation Methods In General (AREA)
EP85101320A 1984-02-17 1985-02-08 Poudres de polymères préparés en émulsion et procédé pour en préparer Ceased EP0154189A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843405651 DE3405651A1 (de) 1984-02-17 1984-02-17 Pulverfoermige emulsionspolymerisate und verfahren zu ihrer herstellung
DE3405651 1984-02-17

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EP0154189A2 true EP0154189A2 (fr) 1985-09-11
EP0154189A3 EP0154189A3 (fr) 1986-12-03

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EP85101320A Ceased EP0154189A3 (fr) 1984-02-17 1985-02-08 Poudres de polymères préparés en émulsion et procédé pour en préparer

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EP (1) EP0154189A3 (fr)
JP (1) JPH07113045B2 (fr)
CA (1) CA1256645A (fr)
DE (1) DE3405651A1 (fr)
ES (1) ES539748A0 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0294663A3 (en) * 1987-06-06 1989-09-06 Rohm Gmbh Spray-died emulsion polymer, process for its preparation and the use of such a prepared composition
EP0299344A3 (en) * 1987-07-17 1989-09-06 Rohm Gmbh Low dust spray-dried emulsion polymerisate and its preparation and use processes
EP0262326A3 (en) * 1986-08-07 1989-09-06 Rohm Gmbh Process for preparing a redispersible resin powder
EP0335365A3 (fr) * 1988-03-29 1991-03-06 Mitsubishi Rayon Co., Ltd. Agent facilitant la préparation de résine thermoplastique, et composition de résine thermoplastique le contenant
EP0715020A1 (fr) * 1994-12-02 1996-06-05 Lefatex Chemie GmbH Agent de revêtement pour des surfaces de papier
EP1201692A1 (fr) * 2000-10-25 2002-05-02 Rohm And Haas Company Procédé de préparation d'agent antichoc pulvérulant
WO2017040893A1 (fr) * 2015-09-04 2017-03-09 Sabic Global Technologies B.V. Compositions en poudre, procédé de préparation d'articles et de revêtements à partir des compositions en poudre, et articles ainsi préparés
US9724302B2 (en) 2010-04-09 2017-08-08 Pacira Pharmaceuticals, Inc. Method for formulating large diameter synthetic membrane vesicles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3702997A1 (de) * 1987-02-02 1988-08-11 Roehm Gmbh Verfahren zur herstellung eines redispergierbaren kunststoffpulvers
MXPA02011812A (es) 2001-12-14 2005-08-26 Rohm & Haas Particulas de polimeros multimodales y sus usos.
MXPA02011785A (es) 2001-12-14 2005-08-26 Rohm & Haas Procesos para preparar composiciones de particulas de polimeros multimodales.

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DE2101808C2 (de) * 1971-01-15 1984-09-13 Röhm GmbH, 6100 Darmstadt Verarbeitungshilfsmittel für Hart-PVC-Formmassen
US3784498A (en) * 1972-04-21 1974-01-08 Sinclair Koppers Co Process for preparing low emulsifier synthetic latex
JPS5826962B2 (ja) * 1975-06-16 1983-06-06 三菱レイヨン株式会社 ラテツクスケイギヨウシユウザイノ セイゾウホウホウ
CA1117677A (fr) * 1977-03-17 1982-02-02 David R. Gehman Latex polymerique plastifie a l'interieur
DE3017543A1 (de) * 1980-05-08 1981-11-26 Bayer Ag, 5090 Leverkusen Waessrige dispersionen auf basis von (meth)acrylsaeurealkylester-polymerisaten mit zwei ausgepraegten, praktisch sich nicht ueberlappenden maxima in der teilchengroessenverteilung innerhalb spezieller teilchengroessenbereiche, sowie verfahren zu ihrer herstellung und ihre verwendung
DE3147008A1 (de) * 1981-11-27 1983-06-01 Röhm GmbH, 6100 Darmstadt Verfahren zur herstellung von waessrigen, hochkonzentrierten bimodalen kunststoffdispersionen
US4461869A (en) * 1981-12-30 1984-07-24 The B. F. Goodrich Company Process for making low fusion dispersion resins

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0262326A3 (en) * 1986-08-07 1989-09-06 Rohm Gmbh Process for preparing a redispersible resin powder
EP0294663A3 (en) * 1987-06-06 1989-09-06 Rohm Gmbh Spray-died emulsion polymer, process for its preparation and the use of such a prepared composition
US5017631A (en) * 1987-06-06 1991-05-21 Rohm Gmbh Method for making a spray dried emulsion polymer
EP0299344A3 (en) * 1987-07-17 1989-09-06 Rohm Gmbh Low dust spray-dried emulsion polymerisate and its preparation and use processes
EP0335365A3 (fr) * 1988-03-29 1991-03-06 Mitsubishi Rayon Co., Ltd. Agent facilitant la préparation de résine thermoplastique, et composition de résine thermoplastique le contenant
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DE3405651C2 (fr) 1990-04-12
EP0154189A3 (fr) 1986-12-03
JPS60195110A (ja) 1985-10-03
JPH07113045B2 (ja) 1995-12-06
CA1256645A (fr) 1989-06-27
ES8601246A1 (es) 1985-11-16
DE3405651A1 (de) 1985-08-22
ES539748A0 (es) 1985-11-16

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